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The photoionization curves and the threshold energies for the molecule and several abundant fragment ions of CF 4 C 2 F 6 , C 3 F 8 , C 4 F 10 , CF 3 H, CF 3 Cl, CF 3 Br, and CF 3 I have been measured. The threshold energies are correlated and the ionic heats of formation and some bond dissociation energies are calculated. It is apparent that the values obtained for theCF   3  +    ions are not the adiabatic ones, but include large amounts of excess energy. This excess is the lowest for theCF   3  +    from CF 3 I for which an explanation is suggested. Assuming that the excess is not zero for the last compound we obtain the following upper limits:   Δ  H   f  0  °(CF   3    )    +   ⩽  +  365.3kJ mol     -  1    =  +  87.3    kcalmol    -  1; I (CF 3 ) + ⩽ 8.62 eV; I (C 2 F 5 ) + ⩽ 8.72 eV; I (C 3 F 7 ) + ⩽ 8.70 eV; I (C 4 F 9 ) + ⩽ 8.68 eV. From the mean value D(C  p  - C  p  ) = 402 ±2 kJ mol -1 = 96.0 ± 0.5 kcal mol -1 the bond dissociation energies D( C   p  - C   s  ) = 363 ± 3 kJ mol -1 = 86.8 ± 0.8 kcal mol -1 and D(C  s  - C  s  ) = 337 ± 4 kJ mol -1 = 80.6 ± 1.0 kcal mol -1 and D( C   p  - F) = 525 kJ mol -1 = 125.7 kcal mol -1 are calculated.

Mass spectrometric study of the photoionization of some fluorocarbons and trifluoromethyl halides